Separation of R-1233 from hydrogen fluoride

ABSTRACT

The invention relates to a process for separating monochloro-trifluoropropenes such as HCFC-1233 from azeotrope or azeotrope like combinations with HF. The process employs a cold, liquid phase separations and multiple azeotropic distillation trains.

This application is a Continuation-In-Part of U.S. application Ser. No.13/257,740 filed Sep. 20, 2011, which claims priority to Internationalapplication serial number PCT/US10/27409 filed Mar. 16, 2010 whichdesignated the United States which claims priority of U.S. provisionalapplication Ser. No. 61/162,789 filed Mar. 24, 2009, all incorporatedherein by reference.

FIELD OF THE INVENTION

The present invention relates to a separation method for isolatingmonochloro-trifluoropropenes such as 1,1,1-trifluoro-3-chloro-2-propene(HCFC-1233zd) from azeotropic or near azeotropic streams ofmonoehloro-trifluoropropenes and hydrogen fluoride. The method of thepresent invention makes use of chilled, liquid phase separation combinedwith azeotropic distillations to isolate puremonochloro-trifluoropropenes such as HCFC-1233zd.

BACKGROUND OF THE INVENTION

With continued regulatory pressure there is a growing need to producemore environmentally sustainable replacements for refrigerants, heattransfer fluids, foam blowing agents, solvents, and aerosols with lowerozone depleting and global warming potentials. Chlorofluorocarbon (CFC)and hydrochlorofluorocarbons (HCFC), widely used for these applications,are ozone depleting substances and are being phased out in accordancewith guidelines of the Montreal Protocol. Hydrofluorocarbons (HFC) are aleading replacement for CFCs and HCFCs in many applications; though theyare deemed “friendly” to the ozone layer they still generally possesshigh global warming potentials. One new class of compounds that has beenidentified to replace ozone depleting or high global warming substancesare halogenated olefins, such as hydrofluoroolefins (HFO) andhydrochlorofluoroolefins (HCFO). The HFOs and HCFOs provide the lowglobal warming potential and zero or near zero ozone depletionproperties desired.

Because of the presence of alkene linkage it is expected that the HFOsand HCFOs will be chemically unstable, relative to HCFCs or CFCs. Theinherent chemical instability of these materials in the lower atmosphereresults in short atmospheric lifetimes, which provide the low globalwarming potential and zero or near zero ozone depletion propertiesdesired.

U.S. Pat. No. 6,013,846 discloses azeotropes of HF and 1233zd andmethods for separating such azeotropes from mixtures of HF and 1233zdwhich are HF rich or 1233zd rich. The method comprises treating amixture rich in HF relative to the azeotrope of 1233zd and HF in adistillation (rectification) column to obtain a distillate containingthe azeotrope and a bottoms product of relatively pure HF

SUMMARY OF THE INVENTION

In the present invention, a method was discovered for separatingazeotrope or near azeotrope compositions of monochloro-trifluoropropenesand HF, preferrably 1.233zd and HF. The method of the present inventionis also effective in separating other isomers of 1233, such as 1233xf(1,1,1-trifluoro-2-chloro-3-propene) from azeotrope or azeotrope likecombinations with HF. The azotrope or near azeotrope combination ofmonochloro-trifluoropropenes and HP could be produced, for example, in aliquid phase fluorination reaction of 1,1,1,3,3-pentachloropropane(240fa) or 1,1,3,3-tetrachloro-2-propene (referred to hereinafter as(1230za). The 1230za is of special interest as a starting material sinceit has been shown to fluorinate readily in the liquid phase without acatalyst, as taught in U.S. Pat. No. 5,877,359. One of the problemsassociated with the production of the trans isomer of 1233zd, thepreferred isomer of the present invention, is that it has nearly thesame boiling point (18-20° C.) as HP and azeotropes or near azeotropescan form with HF.

The fluorination of 240fa 1230za can take place in a catalyzed oruncatalyzed liquid phase reaction. Typically the liquid phasefluorination reactor is coupled to a rectification column(s). The feedto the fluorination reactor consists of an organic chlorocarbon and HPwhich react to form a hydrofluorocarbon (HIV) or hydrochlorofluorocarbon(HUG) that is more volatile than the original chlorocarbon. The HFC orHCFC product can be removed from the reaction mixture as a gas alongwith by-product HCl and some unreacted HF. The rectification column iscoupled to the reactor to separate unreacted organic and underfluorinated organic compounds from HCl. The overhead from therectification column is an azeotrope or near azeotrope combination of1233zd and which also contains the HCl by-product of the reaction. Inthe case of 1233zd, the organic feedstock chlorocarbon to thefluorination reactor can be 1,1,3,3 tetrachloropropene (1230za) or1,1,1,3,3 pentachloropropane (240fa).

In the present application “distillation column” and “rectificationcolumn” are sometimes used interchangeably. Actually, however, arectification column is a specific type of distillation column. In mostdistillation columns the material to be distilled is fed to the middleof the column; below the feed point is called the stripping section andabove the feed point is called the rectification section. Reference ismade herein to a rectification column when the material to be distilledis fed to the bottom of the “distillation column.”

The process of the present invention uses azeotropic distillationcolumns to separate 1233zd from HF. The composition of the feed to theazeotropic columns must have either HF or F1233zd in substantial excessof its azeotropic composition. In the method of the present invention,such streams are provided by first separating, by distillation, HCl fromthe azeotrope or near azeotrope 1233zd/HF that exits from the overheadof the rectification column. The azeotrope or near azeotrope combinationof 1233zd/HF is than cooled to a temperature sufficient to provideseparation into an HF rich phase and a 1233zd rich phase. The HF richphase is separated from the 1233zd rich phase in a liquid phaseseparator. Thereafter, the HF rich phase is fed to a first azeotropicdistillation column that removes the azeotrope as an overhead and pureHF as the bottoms. The 1233zd rich phase is sent to a distillation trainthat includes a second azeotropic distillation column. The distillationtrain separates the 1233zd/HF azeotrope from 1233zd via azeotropicdistillation and also separates impurities from the 1233zd to provide astream of substantially pure 1233zd.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of a typical process in accordance with thepresent invention.

DETAILED DESCRIPTION OF THE INVENTION

The object of the present invention is to provide a means for separatingmonochloro-trifluoropropenes, preferably1,1,1-trifluoro-3-chloro-2-propene (1233zd) and more preferably thetrans isomer of 1233zd referred to hereinafter as “1233zd-t”, from HFwhen the two occur in an azeotrope or near azeotropic combinations.Azeotropic distillation is used to separate RIF and 1233zd, preferably1233zd-t, since they have very similar boiling points. The azeotropicmixture is typical of what is produced from liquid phase reactions thatproduce 1233zd from organic chlorocarbon feedstocks such as 1230za and240fa. The azeotrope or near azeotrope compositions form when thereactor system uses a rectification column coupled to the reactor toseparate out unreacted unreacted feed organic, and under fluorinatedorganics from the vapor produced. The rectification column separates thevapor effluent from the reactor and produces a gas phase combination ofHF and 1233zd, preferably 1233zd-t, in a ratio near the azeotropic ratioof HF and 1233zd. U.S. Pat. No. 6,013,846 discloses that this is ratiois about 2.33 moles HF per mole of 1233zd at 50° C. The overhead fromsuch rectification columns would also contain HCl.

In accordance with the present invention, the azeotropic or nearazeotropic combination of 1233zd, preferably 1233zd-t, and HF from thetop of the rectification column is fed to a distillation column whereHCl is removed. The HCl removal distillation column is typicallyoperated at pressures of from about 100 psig to 300 psig. The bottomsfrom the HCl removal distillation column comprises the azeotrope orazeotrope like combination of 1233zd, preferably 1233zd-t, and HF. Thisbottoms stream is cooled sufficiently to provide that two phases form.Each phase contain the azeotrope or azeotrope like 1233zd/HF andindependently HE or 1233zd. Thus the overall composition of each streamdiffers significantly from the azeotrope. One phase, the lighter phase,is rich in HF and the second phase, the heavier phase, is rich 1233zd,preferably 1233zd-t. The two phase mixture is fed to a liquid phaseseparator. The liquid phase separator can be operated at temperatures offrom about −60° C. to +50° C., preferably from about −20° to +10° C. Thelighter liquid phase has HF in substantial excess over the azeotropecomposition. This HF rich phase is sent to a first azeotropicdistillation column where azeotropic 1233zd/HF is removed as overheadand relatively pure HF removed as the bottoms. The azeotropic 1233zd/HFoverhead is recycled to cooled and fed to the phase separator and the HEbottoms stream is recycled to the reactor. The heavy phase from theliquid phase separator comprises a substantial excess of 1233zd-t,preferably 1233zd-t, over the azeotropic composition. This stream issent to a distillation train comprising a series of distillationcolumns. The first distillation column removes as an overhead any veryvolatile impurities such as HCl or over fluorinated HFC's. The bottomsof this column is sent to a second azeotropic column. This secondazeotropic distillation column removes a 1233zd/HF azeotrope as overheadand crude 1233zd, preferably 1233zd-t, as a bottoms. The overhead can berecycled to be cooled and fed to the liquid phase separator. The bottomsis sent to a product recovery distillation column that recovers purified1233zd, preferably 1233zd-t, as overhead and any heavy, organicimpurities such as the cis-isomer of 1233zd as a bottoms stream. Theprocess of the present invention provides a method whereby relativelypure 1233zd, preferably 1233zd-t, can be separated from an azeotropeazeotrope like combination of 1233zd and HF.

FIG. 1 show a schematic of a process in accordance with the presentinvention. The feeds to the reactor system are typically HF (Stream 1)and an organic stream, either 240fa or 1230za (Stream 2). The reactor(R101) may or may not contain a catalyst. The selective products of thereaction are 1233zd and HCl. These would exit the reaction system fromthe top of a rectification Column (C101) along with enough HF to beclose to its azeotropic ratio with 1233zd (Stream 3).

Column C102 removes the HCl as an overhead product (Stream 4). Thiscould be done at pressures anywhere from 100 psig to 300 psig. Thebottoms from this column (stream 5) would then be cooled in a heatexchanger (E105) and sent to a liquid phase separator (V102). The liquidphase separator could operate at temperatures from −60° C. to +50° C. Apreferred temperature range would be −20° C. to 10° C. The lighterliquid phase (Stream 7) would have HF in substantial excess over theazeotropic composition. This phase is sent to a first azeotropicdistillation column (C103) that removes the HF/F1233zd azeotrope asoverhead (Stream 8) and relatively pure HF as a bottoms (Stream 9). Theazeotropic composition is recycled to be cooled and fed to the phaseseparator and the HF can be recycled to the reactor R101.

The heavy phase (Stream 6) from the phase separator contains 1233zd insubstantial excess over the 1233zd/HF azeotropic composition. Thisstream is sent to a series of distillation columns. The first column(C104) is a purification column which removes as an overhead (Stream 10)any very volatile impurities such as residual HCl or over fluorinatedHFC's. The bottoms of the first column (Stream 11) is then sent to thesecond azeotropic distillation column (C105). This azeotropicdistillation column removes a 1233zd/HF azeotrope as overhead (Stream12) and a crude 1233zd stream as bottoms (Stream 13). The overheadstream can be recycled to be cooled and fed to the liquid phaseseparator V102. The bottoms stream is sent to a product recoverydistillation column (C106) that recovers pure 1233zd, preferably1233zd-t, as overhead (Stream 14) and any organic impurities such as thecis isomer of 1233zd as a bottoms (Stream 15).

As shown in Example 1, the heavy phase (stream 6) effluent from thephase separator can have a relatively low concentration of HF. Recoveryof such small amounts of HF may not be desirable. Consequently, analternative to distillation of that stream to remove and recover the HFis to remove the HF using absorption into liquid absorbent such as wateror caustic, NaOH and/or KOH, or adsorption onto a solid adsorbent suchas alumina and discard the adsorbed HF. The HF (acid) free streamremaining would flow to the first column (C104). The lighter phase(stream 7) contains a significant amount of F1233zd-t. An alternative totreatment in a dedicated azeotropic distillation column (C103) for theheaver phase is to recycle this stream to the bottom portion of columnC101 (i.e. the rectification column) where the HF is separated and sentback to the reactor and the F1233zd/HF azeotrope is distilled overhead.

EXAMPLES Example 1

A set of experiments were conducted to determine the liquid-liquidequilibrium in an HF-F1233zd system. A mixture of F1233zd and HF wereequilibrated at four different temperatures. Samples of bottom and topphases were analyzed. The following results were obtained:

TABLE 1 Upper Lower Layer (wt %) Layer (wt %) T (Deg C.) HF F1233zd-t HFF1233zd-t −30 75.72 24.28 0.85 99.15 −15 71.16 28.84 1.18 98.82 0 67.8632.14 1.72 98.28 30 56.26 43.74 4.12 95.88

Example 2

An example of a material balance of the relevant part of the process fora phase separator operated at −20 C is shown in Table 1 The streamnumbers refer to those used in FIG. 1. As the table shows, the phaseseparation will produce two phases far enough removed from theazeotropic composition that aeotropic distillation can be used toisolate both pure HF and pure 1233zd.

TABLE 2 kg/hr 10 11 12 13 5 6 7 8 9 Lights Lights F12333zd F1233zd FeedOrg Ph HF Ph HF Ovhd HF Bttms Ovhd Btms Ovhd Bttms 1233zd-t 130.45134.93 25.32 25.32 0.00 0.00 134.93 4.48 130.45 1233zd-c 13.05 13.402.52 2.52 0.00 0.00 13.40 0.36 13.05 245fa 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 HF 57.20 1.79 68.29 11.10 57.20 0.00 1.79 1.79 0.00 HCl0.36 0.36 0.00 0.00 0.00 0.36 0.00 0.00 0.00 Total 201.06 150.48 96.1338.93 57.20 0.36 150.11 6.62 143.50 Temp (C.) −20 −20 −20 47 68 −28 8065 65 Press (psia) 40 40 40 65 66 130 130 50 88

While the present invention has been described with respect toparticular embodiments thereof, it is apparent that numerous other formsand modifications of this invention will be obvious to those skilled inthe art. The appended claims and this invention generally should beconstrued to cover all such obvious forms and modifications, which arewithin the true spirit and scope of the present invention.

The invention claimed is:
 1. A method for producingmonochloro-trifluoropropene from an azeotrope or azeotrope likecombination of monochloro-trifluoropropene and HF which comprises (a)distilling a reaction mixture comprising hydrogen fluoride,monochloro-trifluoropropene, and hydrogen chloride to remove hydrogenchloride as overhead and a bottoms stream, (b) cooling the bottomsstream to form two liquid phases, (c) separating said two liquid phasesin a liquid phase separator into a first light phase comprising hydrogenfluoride in excess over an azeotrope or azeotrope like combination ofmonochloro-trifluoropropene and hydrogen fluoride and a second heavyphase comprising an excess of monochloro-trifluoropropene over anazeotrope or azeotrope like combination of monochloro-trifluoropropene,(d) distilling said first light phase in a distillation column toproduce a top stream of an azeotrope of monochloro-trifluoropropene andhydrogen fluoride and a bottoms stream of hydrogen fluoride, (e)contacting said second heavy phase with an absorbent to remove HFfollowed by distilling said second heavy phase in a distillation trainto provide a monochloro-trifluoropropene stream.
 2. The method of claim1 wherein said reaction mixture comprising hydrogen fluoride,monochloro-trifluoropropene, and hydrogen chloride is formed by reacting1,1,1,3,3-pentachloropropane and/or 1,1,3,3-tetrachloro-2-propene andhydrogen fluoride in a reactor.
 3. The method of claim 1 wherein saidbottoms stream is cooled to from about −60 to +30 degrees C.
 4. Themethod of claim 1 wherein said top stream of an azeotrope ofmonochloro-trifluoropropene and hydrogen fluoride is recycled to saidliquid phase separator.
 5. The method of claim 2 wherein said bottomsstream of hydrogen fluoride is recycled to said reactor.
 6. The methodof claim 1 wherein said distillation train comprises a purificationdistillation column to separate said excess ofmonochloro-trifluoropropene over an azeotrope or azeotrope likecombination of monochloro-trifluoropropene and hydrogen fluoride into avolatile impurities top stream and a bottoms stream which is sent to asecond azeotropic distillation column to provide a top stream of anazeotrope of monochloro-trifluoropropene and hydrogen fluoride and abottoms stream of crude monochloro-trifluoropropene and a recoverydistillation column to separate said bottoms stream of crudemonochloro-trifluoropropene into a top stream of purifiedmonochloro-trifluoropropene and a bottoms stream of heavy impurities. 7.The method of claim 1 wherein said monochloro-trifluoropropene isselected from the group 1,1,1-trifluoro-3-chloro-2-propene and1,1,1-trifluoro-2-chloro-3-propene.
 8. The method of claim 6 whereinsaid purified monochloro-trifluoropropene is the trans isomer of1,1,1-trifluoro-3-chloro-2-propene.
 9. The method of claim 1 whereinsaid absorbent is a liquid absorbent selected from the group consistingof water, aqueous NaOH, aqueous KOH and mixtures thereof.
 10. The methodof claim 1 wherein said absorbent is an alumina solid absorbent.
 11. Amethod for producing monochloro-trifluoropropene from an azeotrope orazeotrope like combination of monochloro-trifluoropropene and HF whichcomprises (a) distilling a reaction mixture comprising hydrogenfluoride, monochloro-trifluoropropene, and hydrogen chloride in arectification column to remove hydrogen chloride as overhead and abottoms stream, (b) cooling the bottoms stream to form two liquidphases, (c) separating said two liquid phases in a liquid phaseseparator into a first light phase comprising hydrogen fluoride inexcess over an azeotrope or azeotrope like combination ofmonochloro-trifluoropropene and hydrogen fluoride and a second heavyphase comprising an excess of monochloro-trifluoropropene over anazeotrope or azeotrope like combination of monochloro-trifluoropropene,(d) recycling said first light phase to said rectification column, (e)distilling said second heavy phase in a distillation train to provide amonochloro-trifluoropropene stream.
 12. The method of claim 11 whereinsaid reaction mixture comprising hydrogen fluoride,monochloro-trifluoropropene, and hydrogen chloride is formed by reacting1,1,1,3,3-pentachloropropane and/or 1,1,3,3-tetrachloro-2-propene andhydrogen fluoride in a reactor.
 13. The method of claim 11 wherein saidbottoms stream is cooled to from about −60 to +30 degrees C.
 14. Themethod of claim 11 wherein said distillation train comprises apurification distillation column to separate said excess ofmonochloro-trifluoropropene over an azeotrope or azeotrope likecombination of monochloro-trifluoropropene and hydrogen fluoride into avolatile impurities top stream and a bottoms stream which is sent to asecond azeotropic distillation column to provide a top stream of anazeotrope of monochloro-trifluoropropene and hydrogen fluoride and abottoms stream of crude monochloro-trifluoropropene and a recoverydistillation column to separate said bottoms stream of crudemonochloro-trifluoropropene into a top stream of purifiedmonochloro-trifluoropropene and a bottoms stream of heavy impurities.15. The method of claim 11 wherein said monochloro-trifluoropropene isselected from the group 1,1,1-trifluoro-3-chloro-2-propene and1,1,1-trifluoro-2-chloro-3-propene.
 16. The method of claim 15 whereinsaid monochloro-trifluoropropene is the trans isomer of1,1,1-trifluoro-3-chloro-2-propene.